EP0507117A1 - Matières de moulage ABS à répartition bimodale des dimensions des particules de caoutchouc - Google Patents

Matières de moulage ABS à répartition bimodale des dimensions des particules de caoutchouc Download PDF

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Publication number
EP0507117A1
EP0507117A1 EP92104130A EP92104130A EP0507117A1 EP 0507117 A1 EP0507117 A1 EP 0507117A1 EP 92104130 A EP92104130 A EP 92104130A EP 92104130 A EP92104130 A EP 92104130A EP 0507117 A1 EP0507117 A1 EP 0507117A1
Authority
EP
European Patent Office
Prior art keywords
graft
weight
abs
rubber
matrix
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP92104130A
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German (de)
English (en)
Other versions
EP0507117B1 (fr
Inventor
Ehrenfried Dr. Baumgartner
Jürgen Hofmann
Rudolf H . Dr. Jung
Rainer Dr. Moors
Hansjoerg Schaech
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
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Publication date
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Publication of EP0507117A1 publication Critical patent/EP0507117A1/fr
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Publication of EP0507117B1 publication Critical patent/EP0507117B1/fr
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Expired - Lifetime legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/08—Copolymers of styrene
    • C08L25/12—Copolymers of styrene with unsaturated nitriles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
    • C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group

Definitions

  • the invention describes an ABS molding composition with a bimodal distribution of the rubber particle size, the rubber phases of which are produced exclusively in solution or bulk polymerization.
  • ABS molding compositions with bimodal rubber particle size distribution are known.
  • at least one rubber phase is produced in emulsion polymerization, which is described, inter alia, in the publications below.
  • the individual structure of the rubber particles influences the physical properties of the ABS molding compounds.
  • rubber particles polymerized in solution or in bulk and obtained by precipitation and rubber particles polymerized in emulsion. These are referred to as LABS particles or as EABS particles; A description of the production can be found in documents (1) and (2).
  • the LABS particles described in (1) contain inclusions of the polymer matrix in the rubber and are usually formed and grafted in bulk, bulk suspension or solution polymerization. These processes start from a pre-formed (base) rubber, which is dissolved in the monomer and optionally the solvent and then subjected to the polymerization, the LABS particles forming during the phase inversion.
  • the rubber particles obtained in this way are usually larger than 500 nm and reduce the surface gloss of ABS molding compositions (9-11).
  • the EABS particles mentioned in (2) are generally small, solid rubber particles. Rubber particles with this structure are usually formed and grafted in an emulsion process. The rubber particles are obtained by polymerizing e.g. Butadiene is prepared in an aqueous phase with the aid of suitable emulsifiers. The aqueous rubber latex is then grafted with the monomers which are also present in the matrix, the idea being that the physical entanglement of the graft branches with the matrix polymers brings about a good connection of the tough and hard phases, which increases the toughness of the ABS molding compositions is crucial.
  • the rubber particles produced in this way generally have a particle diameter of less than 500 nm and provide high-gloss surfaces in finished ABS parts.
  • the object of the invention is to create ABS products with a favorable ratio of toughness and gloss and with a light intrinsic color, as is known from pure solution ABS.
  • Solution ABS with rubber particles whose diameter is less than 500 nm can e.g. can be obtained in that the polymerization is carried out in a plurality of series-connected tubular reactors which operate essentially without backmixing, phase inversion occurring in one of the reactors.
  • the reaction temperature should take place at 90 ° C or less until the phase inversion and correspondingly easily decomposing radical initiators (e.g. tert-butyl perester) should be used.
  • ABS coarse-particle solution
  • particle diameters up to 10,000 nm is generally known and e.g. can be found in the publications mentioned at the beginning.
  • polystyrene acrylonitrile and / or polymethyl methacrylate are, for example, polystyrene acrylonitrile and / or polymethyl methacrylate. Both polymers are also made by a solution or bulk polymerization process.
  • the polystyrene acrylonitrile generally has an acrylonitrile content of between 10 and 40% by weight of polymethyl methacrylate or copolymers of methyl methacrylate with other acrylic esters up to an acrylic ester content of about 20% by weight can also be used.
  • the molding compositions obtained by the process according to the invention can be processed by the known methods of thermoplastic processing, i.e. by extrusion, injection molding, calendering, blow molding, pressing or sintering; Moldings are particularly preferably produced from the molding compositions produced by the process according to the invention by injection molding.
  • a product (G) with the following properties was used as the solution ABS with large rubber particles:
  • the molding compound obtained in the counter-test no longer meets the requirements for surface gloss that are made.
  • Product G was used as the solution ABS with large rubber particles.
  • a product (E) which had the following properties was used as the emulsion ABS with small rubber particles:
  • the latex obtained was agglomerated by adding 25 parts of an emulsion of a copolymer of 96 parts of ethyl acrylate and 4 parts of methacrylic acid amide with a solids content of 10% by weight, an average particle size of 300 nm being achieved. After adding 40 parts of water, 0.4 part of Na-C14 alkyl sulfonate and 0.2 part of potassium peroxodisulfate, 38 parts of a mixture of styrene and acrylonitrile were fed in a ratio of 70:30 within 4 hours and polymerized at 75 ° C. Sales related on styrene-acrylonitrile, was practically quantitative.
  • the graft rubber dispersion obtained was precipitated using calcium chloride solution and washed with distilled water.
  • Solution ABS product G was mixed with the emulsion ABS product E as granules in the stated weight ratio, melted together in the extruder at 280 ° C., mixed and granulated as a mixed product.
  • the properties of the mixtures obtained are summarized in the following comparative experiments:
  • the products obtained in the comparison test are colored deeper yellow than the ABS products obtained in the examples according to the invention.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Graft Or Block Polymers (AREA)
EP92104130A 1991-03-30 1992-03-11 Matières de moulage ABS à répartition bimodale des dimensions des particules de caoutchouc Expired - Lifetime EP0507117B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4110459 1991-03-30
DE4110459A DE4110459A1 (de) 1991-03-30 1991-03-30 Abs-formmassen mit bimodaler kautschukpartikelgroessenverteilung

Publications (2)

Publication Number Publication Date
EP0507117A1 true EP0507117A1 (fr) 1992-10-07
EP0507117B1 EP0507117B1 (fr) 1996-12-04

Family

ID=6428540

Family Applications (1)

Application Number Title Priority Date Filing Date
EP92104130A Expired - Lifetime EP0507117B1 (fr) 1991-03-30 1992-03-11 Matières de moulage ABS à répartition bimodale des dimensions des particules de caoutchouc

Country Status (3)

Country Link
US (1) US5434218A (fr)
EP (1) EP0507117B1 (fr)
DE (2) DE4110459A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0872520A1 (fr) * 1997-04-15 1998-10-21 Bayer Ag ABS moulages avec une bonne résistance aux chocs qui sont produits sans émulsion

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4443966A1 (de) * 1994-12-09 1996-06-13 Basf Ag Thermoplastische Formmassen
DE19518025A1 (de) * 1995-05-17 1996-11-21 Bayer Ag Thermoplastische ABS-Formmassen
KR100408109B1 (ko) * 2000-12-28 2003-12-01 제일모직주식회사 진공성형성이 우수한 스티렌계 열가소성 수지 조성물
EP1752478A1 (fr) 2005-08-08 2007-02-14 Basf Aktiengesellschaft Un procédé pour la production d'un copolymère greffé avec une distribution bimodale des particules.
EP1783170A1 (fr) * 2005-10-24 2007-05-09 Basf Aktiengesellschaft Composition thermoplastique de moulage comprenant les matériaux inertes finement divisés.
US20180291195A1 (en) 2015-10-09 2018-10-11 Ineos Styrolution Group Gmbh Electrically insulating thermally conductive polymer resin composition based on styrenics with balanced properties
EP3359592B1 (fr) 2015-10-09 2019-07-24 INEOS Styrolution Group GmbH Composition de résine à base de polymère conducteur électriquement et thermiquement basée sur des styréniques dotée de propriétés équilibrées
EP3359595B1 (fr) 2015-10-09 2019-12-11 INEOS Styrolution Group GmbH Composition de résine à base de polymères thermoconducteurs basés sur des composés styréniques de faible densité
KR102226065B1 (ko) 2018-03-20 2021-03-11 주식회사 엘지화학 열가소성 수지 조성물
CN116554410A (zh) * 2023-05-10 2023-08-08 金发科技股份有限公司 Abs胶粉及其制备方法、abs材料和车辆内饰件

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0412801A1 (fr) * 1989-08-09 1991-02-13 The Dow Chemical Company Procédé de préparation de polymères vinyl-aromatiques renforcés par du caoutchouc
EP0474618A2 (fr) * 1990-09-04 1992-03-11 Monsanto Company ABS à brillance élevée préparé par un procédé en continu

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1745098B2 (de) * 1966-03-21 1974-10-24 Monsanto Co., St. Louis, Mo. (V.St.A.) Polymerisatgemische
US3928494A (en) * 1973-01-09 1975-12-23 Monsanto Co Polyblend of two types of ABS graft polymers and a copolymer matrix
US4250271A (en) * 1979-05-15 1981-02-10 Cosden Technology, Inc. ABS-Type polyblend compositions
EP0103657B1 (fr) * 1982-09-17 1991-03-13 The Dow Chemical Company Résines de type ABS contenant des particules dispersées d'un caoutchouc à haute viscosité en solution et une méthode pour leur préparation
AU594039B2 (en) * 1985-02-01 1990-03-01 Dow Chemical Company, The ABS compositions having trimodal rubber particle distributions and process

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0412801A1 (fr) * 1989-08-09 1991-02-13 The Dow Chemical Company Procédé de préparation de polymères vinyl-aromatiques renforcés par du caoutchouc
EP0474618A2 (fr) * 1990-09-04 1992-03-11 Monsanto Company ABS à brillance élevée préparé par un procédé en continu

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0872520A1 (fr) * 1997-04-15 1998-10-21 Bayer Ag ABS moulages avec une bonne résistance aux chocs qui sont produits sans émulsion

Also Published As

Publication number Publication date
US5434218A (en) 1995-07-18
DE4110459A1 (de) 1992-10-01
EP0507117B1 (fr) 1996-12-04
DE59207600D1 (de) 1997-01-16

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